松香基阴离子交换树脂去除饮用水中有毒含氧卤酸盐的机理研究

The efficient preparation of environmentally friendly, highly efficient functional resins with wide applicability is an important research topic in the field of water treatment. The goal of this project is to produce rosin-derived ion exchange resins for the removal of toxic oxyhalides anion (perchlorate and bromate) from drinking water. First, rosin based cross-linking agent will be synthesised using natural rosin as starting material. The skeleton of the rosin-based resin, formed by the reaction between monomers with different functional groups and rosin based cross-linking agent, will be synthesised by the suspension polymerization method, and rosin-based ion exchange resins will be produced by surface grafting modification of the obtained skeleton. The influence of the pore sizes, specific surface areas, and functional groups of the obtained resins on the exchange /adsorption capacities and thermodynamics will be investigated in single and mixed pollutant systemes. Based on the removal efficiency of the resins and the physicochemical properties of oxyhalides (eg., charge, ionic radius, potential energy), the relationships between the structures and properties of these resins will be assessed. In addition, quantum chemistry calculations and surface analysis techniques will be used to elucidate the exchange/adsorption mechanisms. Rosin is a green, low cost, environmentally friendly material, furthermore, rosin-based anion exchange resins have the advantages of high exchange capacity, high stability, good mechanical strength and selectivity. This project will utilize rosin, a natural resource in Guangxi region, in the production of high value adsorbent materials, and will provide the scientific and technological basis for synthesis and performance evaluation of a new family of green and efficient ion exchange resins.

设计合成绿色、高效、适用性广的功能树脂是水处理领域的重要研究课题之一。本项目以去除饮用水中典型有毒含氧卤酸盐（ClO4¯和BrO3¯）为目标，以天然产物松香为原料合成含聚合基团的松香基交联剂，将其与不同功能单体交联聚合得到松香基树脂骨架，进一步接枝成为离子交换树脂。重点研究在单一及混合污染物体系下，树脂的孔结构（比表面积、孔容及孔径分布）和表面功能基等因素对去除性能及吸附热动力学的影响。将实验参数及理论计算参数（如电荷、水合半径和亲和势等）与树脂吸附性能关联，建立松香基离子交换树脂与卤酸盐之间的构效关系，并借助量子化学理论计算及表面分析技术进一步阐明其去除机制。原料松香无毒、环境友好，用于饮用水中微污染物的控制不会造成二次污染。所合成的离子交换树脂将具有交换容量大、稳定性和选择性好等优点。实施课题有助于高值化利用地区特色松香资源，并为研发高效、绿色的离子交换树脂提供科学依据和技术基础。

设计合成绿色、高效、适用性广的功能吸附/离子交换树脂是水处理领域的重要研究课题之一。本项目以去除饮用水中典型有毒含氧卤酸盐[ClO4¯、BrO3¯、ClO3¯、ClO2¯、As(III)和As(V)]、重金属[Pb(II)、Cd(II)、Cu(II)和Zn(II)]和有机微污染物（芳香族化合物、抗生素和三卤甲烷）为目标，采用天然产物松香为原料合成含聚合基团的松香基交联剂及三官能团交联剂，将其与不同功能单体交联聚合得到树脂骨架，进一步接枝成为系列吸附/离子交换树脂（氨化松香基树脂、含叔胺盐酸盐基交联树脂、松香基三烯丙酯交联聚合树脂和聚马来酸酐树脂）。采用扫描电镜、红外、比表面、核磁共振和热重等手段对其进行结构表征。系统考察基于单一和混合污染物体系下，不同吸附影响因素条件的（树脂投加量、pH值、接触时间、离子强度和温度等因素）静态和动态吸附容量、再生循环利用等问题进行了研究。通过细胞增殖实验评价了化学稳定及安全性；基于树脂的孔结构（比表面积、孔容及孔径分布）和表面功能基等因素对去除性能及吸附热动力学的影响，将实验参数及理论计算参数（如电荷、水合半径和亲和势等）与树脂吸附性能关联，建立吸附/离子交换树脂与目标污染物之间的构效关系，并借助了量子化学理论计算及表面分析技术（XPS、EPR和FTIR等手段）进一步阐明其作用机制及贡献大小（离子交换、静电作用和氢键作用）。除此之外，结合饮用水处理工艺-消毒/氧化环节，考察不同消毒工艺对有毒含氧酸盐(亚硒酸盐)的转化动力学。综上所合成的吸附树脂将具有吸附/交换容量大、稳定性和选择性好，绿色安全等优点，本项目的研究成果可有助于高值化利用地区特色松香资源，并为研发高效、绿色的吸附/离子交换树脂提供科学依据和技术基础。